Novel polyfluroalkyl acrylate monomers, polymers and intermediates



United States PatentO 3,409,602 NOVEL POLYFLUOROALKYL ACRYLATE MON MERS, POLYMERS AND INTERMEDIATES Louis G. Anello, Basking Ridge, and Richard F. Sweeney, Randolph Township, Morris County, N.J., assignors to Allied Chemical Corporation, New York, N'.Y., a corporation of New York No Drawing. Filed Oct. 24, 1965, Ser. No. 505,007

17 Claims. (Cl. 260-895) This invention relates to novel polyfluoroalkoxy acrylate monomers, polymers thereof and to certain novel intermediate polyfiuoro alcohols.

Polymers prepared from the monoesters of acrylic acid and its derivatives have been long recognized .as thermoplastic materials whose utility is both wide and varied. For example, acrylic polymers have been successfully employed as aircraft components, internally illuminated commercial signs, vending machine parts, windows, dials, safety shields, motor-boat deck hatches, shoe heels, piano and organ keys, industrial housings, etc. In addition, acrylic polymers, particularly fluorine-containing acrylic polymers, are susceptible to vulcanization to yield'tough, stable polymers suitable for use as gasket material and also as tenacious coating materials. Fluorine-containing acrylic polymers are also known to be useful to impart oleophobic and hydrophobic finishes to various materials, such as cotton cloth or wool fabric. I

We have found a class of acrylic polymers which possess' extremely good oleophobic and hydrophobic properties and which, in addition, exhibit particularly good stability and durability to wear, washings and dry cleanings when applied to porous materials, such as'textiles and the like. The novel class of polymers of the-invention contain recurring polyfiuoroalkoxy acrylate ester units of the formula:

wherein X is H or CH Y is H or F; Z is H or F; Rf and R; which may be the same or different, when taken singly, are prefiuorinated alkyl groups preferably containing 211 carbon atoms inclusive and, when taken together, form a polyfiuorinated cycloalky-l group possessing 4-6 carbon atoms inclusive; n is 0 or 1; mis 0 or '1, provided that when n is 1, m is 0 and when n is 0, m is 1 and provided that when m is 1, Y and Z are alike; and wherein p is 08.

The polymers of the invention, containing therecurring polyfiuoroalkoxy acrylate ester units-as above described, may be homopolymers, in which the indicated recurring units are the only ones present; cop-olymers, in which these recurring units are interspersed with units derived from another polymerizable unsaturated monomer; or heteropolymers, such as terpolymers, in which there are more than two distinct types of recurring units interspersed in the molecule. The homopolymeric prod- 3,409,602 Patented 5, 1 968 nets are thermoplastic and, depending on the molecular weight, vary from soft rubbery compositions to sticky, adhesive-like materials. These polymers are stable, flame resistant, not appreciably soluble in hydrocarbon solvents, such as benzene or xylene, but aresoluble in certain fluorocarbons, such as trifluoroethyl trifluoroacetate. The homopolymeric products, or mixtures thereof, when used as fiber impregnators, impart good oleophobic and hydrophobic properties to such materials. The homopolymers also can be used to cast flexible, transparent, thermoplastic films, which can'be used for wrapping and protective purposes. (30- and heteropolymeric products will reflect properties contributed by the coor heteromonomer(s), but may be hard thermoplastic or thermosetting resins, useful as structural components for a variety of purposes for which prior art acrylic polymers have been employed, a number of which have been mentioned heretofore. Suitable polymerizable monomers for preparation of the coand heteropolymers include the ethylenically unsaturated monomers well known to the art, such as the vinyl compounds, e.g., vinyl esters, vinyl halides, vinyl alkyl keton'es, vinyl alkyl sulfones, some specific examples being vinyl isopropyl sulfone, cinylidene dichloride and N-vinyl urea; olefinic compounds,. such as ethylene, propylene, isobutylene, butadiene and isoprene; aromatic compounds containing olefinic unsaturated groups, such as styrene and alpha-methyl styrene; other acrylic compounds including dissimilar fiuorinated acrylic monomers in accordance with the description of this invention, other halogenated acrylates, acrylic acid amides, acrylic acid nitriles, etc., some specific examples being methyl acrylate, butyl methacrylate, Z-ethylhexyl acrylate, N,N- diethylaminoethyl methacrylate and glycidyl acrylate; other unsaturated acid esters, such as methyl crotonate, methyl maleate, diethyl fumarate, allyl acetate, allyl caprylate and a variety of other unsaturated compounds, such as unsaturated ketones, e.g., alkyl vinyl ketones and the like.

Modifiers, such as mercaptans, may be used to decrease the molecular weight of the polymeric products.

In the following and foregoing discussion of the invention, it is intended that the term acrylic (or acrylate) be understood to comprehend methyl-substituted acrylic (or acrylate), i.e., methacrylic (or methacrylate) as well as acrylic ,(or acrylate). I v

The novel polymers may readily be prepared by polymerizing our novel polyfiuoroalkoxy acrylate monomers of the formula:

arona oYzmocm ono-cL =on, arormpoyzmooz wherein X, -Y, .Z, R R',, m, n and p are as defined above. Preferred species within the generic invention, as. defined above,'are those compounds wherein p'is no greater than 2 and preferably 0; also wherein n is 1; also wherein R} and R, are straight chain perfluorinated alkyl groups and additionally wherein X is H.

In thoseembodiments wherein R; and R' are straight chain perfluorinated alkyl groups, the preferred carbon content for such groups is between 6-10 carbon atoms, inclusive.

Illustrative polyfluoroalkoxy acrylate monomers within the scope of the invention include the following:

1,3-bis(l,1-dihydroperfluoropropoxy)isopropyl acrylate (CF3)2CHOCH2 O H oHoo(3=oH-i (C F 3) 20 H O C a 1,3-bis (hexafiuoroisopropoxy) isopropyl acrylate (crmoHooHi CH,

oHo-o-h=c H: (C FzOzCHO 0%; 1,3 -bis (hexafiuoroisopropoxy isopropyl methacrylate (CFa)2CFOCHfl o H oHoo-( :=oHi (c FshC F o 01 11 1,3 -bis(heptafluoroisopropoxy) isopropyl acrylate CFKCFQACFEOCHQ 0 CH3 oHoo-o=oHz C FAG F940 F20 Cg 1,3-bis (perfiuorohexoxy isoprop yl methacrylate CF3(CFt)aCHaOCHa 0 CH3 CHOC-(I3==C H2 C F3(C F2)3CH2O C 1- l l-dihydroperfiuoropentoxy) 3 -(1,1-dihydroperfluoroheptoxy)isopropyl methacrylate CF3(CF2)a(CH-2)2CH1OCH 0 H OHOC-C=CH2 C Fa( 2)a( r)2 i 1,3-bis(1,1,2,2,3,3-hexahydroperfluoroheptoxy)isopropyl :acrylate 1 ,3 -bis(1 ,1 ,2,2-tetrahydro-3-trifluoromethylp erfluoropentoxy)isopropyl acrylate 1,3-bis(1-hydroperfluorocyclohexoxy)isopropyl methacrylate.

THE POLYMERIZATION REACTION The polymerization technique may be any of the conventional free radical polymerization techniques, such as bulk polymerization, emulsion polymerization and solution polymerization of the appropriate monomers, as defined above. Bulk polymerization may be carried out using cepting that :acr ylate 4 or a peroxide as initiator. Solution polymerization can be carried out employing a suitable solvent, such as tritiuoroethyl trifluoroacetate, and a catalyst, such as a peroxide as initiator.

The preferred method of polymerization is in aqueous emulsion. The polymer can be obtained as an emulsion but is normally obtained as a coagulated polymer or as a mixture of coagulated polymer and emulsion. Emulsification can be elfected by the addition of any one of a number of conventional anionic, non-ionic or cationic emulsifiers, such as sodium lauryl sulfate, the K salt of perfluorosulfonic acid, trimethyltetradeqylammonium chloride, sodium lauryl sulfosuccinate and the like. The emulsions may be easily used to apply thin films of the polymers to various surfaces by conventional methods including the procedure, for example, of coating, as by brushing, dipping of spraying and subsequent airdrying. If the polymer is not recovered in substantially emulsion form it should be further coagulated prior to use in forming films. This may be accomplished by addition of a coagulating agent, such as methanol or acetone, or by mechanical methods, such as freezing. The coagulum, after drying, must be dissolved or dispersed in a suitable solvent prior to use.

Suitable polymerization catalysts or initiators are illustrated by organic or inorganic free radical generators, such as benzoyl peroxide, lauryl peroxide, acetyl peroxide, succinyl peroxide, azobutyronitrile, potassium persulfate, hydrogen peroxide and sodium peroxide.

Polymerization may also be initiated by means of actinic radiation (light) and such is normally accomplished by placing the monomers in an evacuated sealed tube and then exposing the tube to a light source, preferably ultraviolet light, at temperatures ranging from about room temperature to about 125 C.

The reaction time for the polymerization varies over a wide range and for the most part is dependent both upon the temperature employed and upon the nature of the free radical initiator, or the intensity of the actinic radiation, whichever may be the case. Normally polymerization catalyzed by actinic radiation is accomplished in about 10-72 hours. When organic catalysts are employed, polymerization may be accomplished within a period of about 1-10 hours.

Polymerization can be recognized by observing the formation of a rubbeny or hard, tacky material or by observing coagulation or formation of an emulsion out of solution.

some form of light Example 1 To a three-necked, 50 ml. flask, equipped with a dropping funnel, stirrer, thermometer and a reflux condenser were added 15 g. of deionized water, 009 g. of sodium lauryl sulfate and 0.014 g. of potassium persulfate. After flushing the flask contents with nitrogen, 2.5 g. of 1,3-bis (hexafiuoroisopropoxy)isopropyl acrylate were added, with stirring, to the reaction mixture. The temperature of the reaction vessel contents was raised to 50-55 C. and was maintained within that range for a period of about four hours. At the end of this period, an additional 0.014 g. of potassium persulfate were added and the 50-55 C. temperature was maintained for an additional two hours. During the latter period polymerization took place, as evidenced by the formation of a clear, tacky mass in the reaction vessel. The polymeric mass was washed with water and methanol and was then dried under vacuum to give approximately 2 g. yield) of a clear, rubbery polymer. The polymer was found to be insoluble in benzene and xylene and soluble in trifluoroethyl trifluoroacetate.

Examples 2-13 The procedure described in Example 1 is repeated exmonomers, initiators and emulsifiers are varied, as indicated in the following table. In all cases substantially the same results are obtained; that is to say, good yields of a clear, rubbery polymer are obtained.

TABLE I v Example Acrylate Monomer(s) Initiator Einulsilier 2 1,3-bis(1,l-dihydroperfiuoropropoxy)isopropyl aerylate. Potassium persuliate Sodium lauryl sulfate. 3 1,3-bis(hexafluoroisopropoxy)isopropl acrylate Benzoyl peroxide Do. 4 1,3-bis(hexafluoroisopropoxy)isopropyl methacrylate Sodium peroxide Sodium lauryl sultosuccinate. 5 1,3-bis(heptafluoroisopropoxy)isopropyl aerylate.. Potassium persulfate... K salt of perfiuor'osulfonic acid. 6 1,3-bis(perfiuorohexoxy)isopropyl methacrylate.- Azobutyronitrile Trimethyltetradecylammonium chloride. 7 1-(1,l-dihydroperfluoropentoxy)-3(1,l-dihydroperfiuoro- Sodium peroxide. Sodium lauryl s'ulfosucoiuate. heptoxy)isopropyl methacrylate. 8 1,3-bis(1,1,2,2,3,3-hexahydroperfiuoroheptoxy)isopropyl Benzoyl peroxide Sodium lauryl sulfate.

. aer ate. 9 1,3-bis(1,1,2,2-tetral1ydro-3-trifiuoromethylperfluoro- Potassium persulfate K salt of perfluorosulionic acid.

pentoxyfisopropyl acrylate. p 10 1,3-bis(perfluorocyelobutoxy)isopropyl acrylate Azobutyron'itrile Sodium lauryl sulfate. 11 1,3-bis(perfluorocyclopentoxy)isopropyl acrylate Potassium persulfate... Do

Lit-bis(l-hydroperfluorocyclohexoxy)isopropyl methacry Benzoyl peroxide--. l Trimethyltetradecylammonium chloride;

ate.

13 A mixture of 50% by Weight 1,3-bis(hexafluoroisopro- D0 Sodium laurylsul tosuccinate.

poxy)is0propyl aerylate and 1,3bis(hexafluoroisoprov g poxy)isopropylmethaerylate.

PREPARATION OF THE NOVEL POLYFLUORO- idine or quinoline charged to the reaction mixture is gen- ALKOXY ACRYLATE MONOMERS erally about 0.10 to 2.00 parts, preferably 0.5 to 1.5 parts,

The novel polyfluoroalkoxy racrylate monomers, or mixfhi g i reatctant charged tures thereof, are prepared by reacting the corresponding 6 mac empem ure may vary over W1 e range i.e., from below room temperature up to the boiling point 13 bls(polyfluoroa1koxy)lsopmpanol of the formula' of the reaction mixture. Normally a temperature selected R; from about room temperature to 100 C. is utilized with lump n a mild agitation of the reaction mixture. When the anhyl dride form of acrylic acid is employed, the reaction mix- R(OHZ)PCYZOCHZ ture is preferably maintained at about room temperature, CHOH say between about 10-30 C. and still preferably below RKCHMCYZIUOC 2 I about room temperature.

I The esterification reaction is preferably run in the pres- I? I 5 ence of a small mount of a conventional polymerization R; inhibitor, such as hydroquinone, a-pinene and p.-tert iarybutyl catechol, in order to-avoid undesirable premature polymerization which may take place to some extent, particularly at the more elevated temperatures.

40 Reaction times will depend upon the reactivity of the acrylic reactant chosen, the catalyst used, if any, and

- other variables, such as temperature. Substantial ields of Wherem X 15 H or CH3 and Y 15 OH or OCH3' The product may be formed in a period from about g0 minwherein Y, Z, R R' m', n and p are as defined supra, with an acrylic compound of the formula:

acrylic reactant may also be employed in the form of its Utes to several hours anhydride l may be.used Sun by reaFtmg a Recovery and purification of the resulting acrylic ture of glacial flCI'YllC acid and perfluroacetic anhydride 4.) monomer products may be effected [by employing conven 322$: lsopmpanol reactant at below about mom tional procedures, such as solvent extraction, aseries of The molar ratio of the reactants is not critical and -from gg fgga gi steps followed by drxmg 0! Ordinary about 0.1 mole to about 10 moles isopropanol reactant per Exa mp1 e 14 mole acrylic reactant may be employed to secure the desired reaction product. In order to secure highest yields, To a three-necked 100 ml. flask, equipped with a therhowever, a substantially stoichiometric molar ratio should mometer, stirrer, dropping funnel and a water-cooled rebe employed, Le, a mole ratio of about 1:1. flux condenser were added 13.0 g. (0.144 mole) of acrylyl The reaction proceeds quite smoothly in the absence of chloride, g. of CuCl and 0.1 g. of hydroquinone. The a solvent. A suitable solvent, if desired however, may be temperature of the resulting mixture was raised'to about employed to serve as a diluent and to facilitate the reac- 75 0, following which 27.0 g. (0.0689 mole) of 1,3-bis tion at elevated temperatures. Generally speaking, any (hexafluoroisopropoxy)isopropanol (B.P. 56 C./5 mm.) solvent may be employed provided it is inert under the were rapidly added, with stirring, through the dropping conditions of the reaction and provided, of course, that funnel. Temperature in the reaction flask was maintained it is a solvent for the reactants. Illustrative suitable sol- 60 between about 75-80 C. for a period of about six hours. vents include: benzene, pyridine, quinoline, nitrobenzene, At the end of this period the resulting mixture was fracdimethyl aniline, Decalin and 1,1,2-trifiuoro-1,2,2-trichlo tionated through a small spinning band column to give roethane. 25 g. (0.056 mole, 81.0% yield) of l,3-bis(hexafiuoroiso- In order to minimize reaction time, any of the well propoxy)isopropyl acrylate (B.P. 9394 C./5 mm.). known esterification catalysts, such as pyridine, quinoline, Analysis.Calculated for C H F O Percent H, p-toluene sulfonic acid, phosphoric acid, sulfuric acid and 2,24 percent F, 51,12. F d; P t H 23; percent cupric chloride may be employed. The amount of catalyst F 49 7 i's O critical and y range from abOllt t0 y Infrared spectrographic analysis of this compound Weight based on the amounthof p gi a l r g showed peaks consistent with the expected structure. charged. When acrylyl or met acry yl c' oride is use pyridine and quinoline are preferred catalysts since each, Examples 15-25 V in sufficient amounts, acts as a solvent as well. Addition- The procedure of Example 14 is repeated in identical ally, due to their low boiling points, pyridine and quinoapparatus, excepting that isopropanol reactants, acrylic line may be readily separated from the reaction product reactants and acrylic end products, are varied, as indicated in the following table.

by simple distillation. If employed, the amount of pyr- 7.

TABLE II 7 Example Alcohol Reactant Acrylic Reactant Acrylate End Product 1,3-bls(1,1-dihydroperfluoropropoxy)isopropanol Acylic acid 1,3-bisglkl-dihydroperfluoropropoxy)isopropyl acry a e. 16 1,3-bis(hexatluoroisopropoxy)isopropanol Acrylyl chloride 1,3-bis(hexafiuoroisopropoxy)isopropyl acrylate. 17.- do Methacrylyl chloride 1,3-bis(hexafluoroisopropoxy)isopropyl methacrylate. 18 1,3-b s(heptafluoroisopropoxy)isopropanol Acrylic acid 1,3-bis(heptafluoroisopropoxy)isopropyl acrylate. 19.. l,3-bis(perfluorohexoxy)isopropanol. Methaerylic acid. 1,3bis(perfluorohexoxy)isopropylmethaq ylat 20.. 1-(1,1-dihydroperfluoropentoxy)-3-(l,1-d1hydr0per- --d 1-(1,l-dihydroperfluoropentoxy)$-(1.1nihydro erfluoroheptoxy)isopropanol. fluoroheptoxyhsopropyl methacrylate. 21 1,3-bis(1,1,2,2,3,3-hexahydroperfluoroheptoxy)- Acrylyl chloride 1,Ii-bls(1,1,22,3,3-hexahydroperfluoroheptoxy)- ropano lsopropyl acrylate. 22 1,3-bis(1,1,2,2-tetrahydro-3-trifluoromethylperfluoro- Acrylic acid 1,3-bis(1,1,2,2-tetrahydro-3-tritluoromethylperflumopentoxy)isopropanol. pentoxyhsopropyl acrylate. 23 1,3-bis(perfluorocyclobutoxy)isopropanol Acrylylchloride 1,3-b1s(perfluorocyclobutoxy)isopropyl acrylate. 2A..-- 1,3-bis(perfluoroeyclopentoxy)isopropanol d 1,3-bis(perfluorocyclopentoxy)isopropyl acrylate, 25 1,3-bls(l-hdyroperfluorocyclohexoxy)isopropanol... 1,3-b1s(1-hydroperfluorocyclohexoxy)isopropyl methacrylate.

PREPARATION OF THE 1,3-BIS(POLYFLUO RO- Example 26 ALKOXY)ISOPROPANOL INTERMEDIATES To a 100 m-l. four-necked flask, equipped with a drop- The 1,3-bis(polyflu0roalkoxy)isopropanol intermediping funnel, thermometer, condenser and a magnetic stirates are novel compounds and, except for the perfluororer, was charged a mixture of 50 g. (0.298 mole) of hexaalkoxy and perfluorocycloalkoxy species, may be prefluoroisopropanol and g. of distilled water. 16.7 g. d i a one t operation b ti f an l h l (0.298 mole) of potassium hydroxide pellets were added f h f mul to the reaction flask contents at such a rate that the tem- 25 perature did not exceed about 50 C. 12.8 g. (0.138 mole) 1 of epichlorohydrin were then added slowly and the result- (OHDD n ing mixture was heated to 89 C. and maintained at that RKCHmCYZmOH temperature for a period of about one hour. On standing,

an oil layer formed which was separated, washed with water, dried over anhydrous sodium sulfate and vacuum distilled from which were recovered 20.0 g. (0.051 mole) wherein Y, Z, R R", m, n and p are as defined supra, except that Y and Z cannot both be F, with epichloro- 30 hydnn of 1,3-bis(hexafluoroisopropoxy)isopropanol (B.P. 56.5-

(c\H,/CHCHzCl) 57 C./5 mm.).

0 Analysis.-Calculated for C H F O C, 27.6%; H, in an aqueous solution of a base, such as pyridine or %-F 11n C, 27.7%; H, 2.1%;F 589%- sodium hydroxide. Infrared spectrographic analysis confirmed identity of In order to get maximum yields of the desired isothe expected structure. propanol intermediate by this one step operation, an ex- Examples 2742 cess of base relative to the epichlorohydrin should be employed, preferably between about 2.0-3.2 moles of 40 The Procedure descrlbed 111 Example 26 1S Yepfiaied 1n base per mole of epichlorohydrin. Additionally, the conthe Same apparatus exceRting thfrlt f l reactants, base centration of alcohol starting material, relative to the epiand end P are Varled, S l ated 1n the following chlorohydrin reactant, should be in the range of about table. Molar ratios of reactants employed are within the 1.5-4.0 moles of alcohol starting material per mole of preferred ranges indicated supra.

TABLE 111 Example Alcohol Reactant Base End Product 1,l-dihydroperfiuorcpropanol Sodium hydroxide 1, biS(1,l-di ydroperfluoropropoxy)isopropanol. Hexafluoroisopropanol Potassium hydroxide 1,3. is(hexafluorolsopropoxy)iso ro anol.

1,l-dihydroperfluoropentanol and 1,1-dihydroper- .do 1-(l,l dlhydroperfluoropentoxy)-3-(1,1-d1hydrofluoroheptanol. perfluoroheptoxyhsopropanol. 3o 1,1,2,2,3,3-hexahydroperfluoroheptanol Sodium hydr xid g-b ,2i3,3-hemhydroperfluoroheptoxy)- rsopropano 31 l,1,2,2-tetrahydro-3-trifluoromethylperfluoropentanol.. Pyridine 1,3- is(1,1,2,2-tetrahydro-3-trifluoromethylpen'iuompentoxyhsopropanol. 32 1-hydroperfluorocyclohexanol Potassium hydomnde.-. 1,3-blS(l-hydlOIJeIfluOrOCYclOheXOxY)isopl'opanol, epichlorohydrin, preferably between about 2.0-2.5 moles Unsymmetrical(polyfluoroalkoxy)isopropanols may be alcohol starting material per mole epichlorohydrin and prepared by the following procedure. A polyfiuorinated still preferably between about l.75-2.0 moles alcohol alcohol, as above described, is reacted with epichlorohystarting material per mole epichlorohydrin. drin in the presence of base in such a manner as to obtain, Any water soluble base maybe employed in this procas a major Product, a y y ether me ate having ess. Organic bases, such as pyridine, piperidine or tri- 111$ fofmlllfll ethyl amine may be employed; however, inorganic bases, 1 such as sodium hydroxide, potassium hydroxide and the 0H, like are preferred. moan rflzmoomoncn,

The reaction may he conducted at superatmospherrc as well as atmospheric pressure.

Reaction temperatures may vary over a wide range but g f R i. and p are as mdlcated Supra should be somewhat elevated in order to promote a favori can 6 accpmp Shed by t procedure above able reaction rate when operating at atmospheric Pres scribed for reacting these materials, except that the cons the pp te'mperature limitation is the reflux ten} centration of reactants 1s regulated so that the molar rara ture of the mixture In most cases ood results are no of base to eplchlorohydrm hes m the range of L0- P g 2.5 1, preferably 2.0-2.2: 1, and so that the molar ratio of obtained by operating at temperatures between about polyfluorinated alcohol to epichlorohydrin lies in the 50-120 C. and preferably between about 85-115 range of 0.5-1.5:1, preferably 0.9-1.2:1. The glycidyl Product recovery can be effected by simple distillation. ether intermediate can then be isolated and reacted with a dissimilar polyfiuorinated alcohol, as above described, to give an unsymmetrical(polyfluoroalkoxy)isopropanol product.

The 1,3-bis(perfiuoroalkoxy)isopropanol intermediates cannot be prepared from the corresponding perfiuoroalkanols or perfiuorocycloalkanols due to the unavailability or instability of the latter alcohols. They may be prepared, however, by the reaction of epibromohydrin, with the KF adduct of a suitable perfiuorinated ketone or with the KF adduct of a suitable perfiuorinated alkanoyl fluoride.

These reactions must be conducted under anhydrous conditions in the presence of an inert polar solvent, such as acetonitrile, nitrobenzene, diglyme, etc.

The solvent should be employed in a large excess, say in a :1 volume ratio to the amount of KF employed.

' At least a stoichiometric amount of KF should be employed and preferably a stoichiometrical excess, based upon the quantity of ketone or acid fluoride charged.

Reaction temperatures in the range of about 80-120 C. are satisfactory, with temperatures around 100 C. being preferred.

These reactions are most efficiently carried out in closed reatcors under autogenous pressures.

Product recovery involves conventional, ing, drying and distilling steps.

The following illustrate practice of such procedures.

filtering, wash- Example 33 The apparatus consists of a 225 m1. Fisher Porter aerosol compatibility tube (pressure reaction vessel), equipped with a magnetic stirrer, a pressure gauge, an S. S. Hoke valve and an oil bath for controlling reaction temperature. The reaction vessel is charged with ,18 g. (0.31 mole) of anhydrous KF, 100 ml. of anhydrous acetonitrile and 18 g. (0.13 mole) of epibromohydrin. 50 g. (0.30 mole) of hexafluoroacetone are then added to the reatcion mixture, with stirring, by vacuum transfer. The reaction mixture is heated for about 24 hours at 100 C., with continuedstirring following .which the reaction vessel is cooled and vented. The liquid product is filtered, washed with water, dried and distilled. The main product consists of 1,3-bis(heptafluoroisopropoxy)isopropanol.

' Example 34 Example 33, are charged KF, 100 ml. of acetoniepibromohydrin. 83 g.

Into apparatus as described in 10 g. (0.19 mole) of anhydrous trile and 14 g. (0.10 mole) of (0.20 mole) of perfluorooctanoyl fluoride are added to the reaction mixture with stirring. The resulting mixture is heated for 24 hours, with continued stirring, at 105 C. At the end of this period, the reaction vessel is cooled and the liquid product is filtered, washed with water, dried and distilled. The main product consists of 1,3-bis (perfiuorooctoxy)isopropanol.

With the exceptions of 1-hydroperfluorocycloalkanols and those alcohols wherein both Y and Z are P, the various species of starting alcohols embraced by the formula:

wherein Y, Z, R R m, n and p are as indicated supra, belong to known classes of compounds. Many are available commercially and all may be prepared by well known and conventional reactions from available or known precursors, such as the corresponding polyhalogenated ketones. 1-hydroperfluorocycloalkanols are the subject of co-pending, commonly assigned application of Louis G. Anello and Richard F. Sweeney, Ser. No. 424,827, filed Jan. 11, 1965, now Patent No. 3,350,464,

and may be prepared by reduction of the corresponding perfiuorinated cycloalkanone with sodium -borohydride in the presence of an inert polar solvent at temperatures in the range of about 20 70 C. Those alcohols wherein both Y and Z are F are, as noted above, either not known to exist or are not known to be sufiiciently stable to permit reaction according to the processes described herein. The corresponding perfluorinated alkanones and cycloalkanones, as well as the corresponding perfiuorinated alkanoyl fluorides, which serve as starting materials for the perfiuoroalkoxy and perfluorocycloalkoxy species of isopropanol intermediates, are also known classes of compounds which are ,either commercially available or may be prepared by standard techniques.

UTILITY OF THE POLYMERICPRODUCTIS The homopolymeric products may be used to impart oil and water-repellent properties to a variety of porous materials, such as textiles,- fibers, fabrics of natural or synthetic origin, e.g., cotton cloth, nylon and a variety of other substrates, such as paper, wood, metal and the like. The polymer is applied as a coatingto such materials by conventional techniques, such as spraying, brushing or dipping procedures. The polymers may be used as an aqueous emulsion or in solution with a-suitable solvent, followed by drying of the coated material to remove water or the solvent.

In the following example, these-called 3M Oil Repellency Test was used to evaluate the oil repellent properties of a cotton fabric treated with representative homopolymeric products. This test was performed as described by E. J. Grajeck et al., Textile Research -Journal,'April 1962, pp. 323-324. Water repellency was evaluated by the Spray Test Method (ASTM-D583-58).

Example 35 Samples of x 80" undyed cotton print cloth were dipped into a solution comprising 4% by weight of the 1,3 bis(hexafiuoroisopropoxy)isopropyl acrylate polymer prepared in Example 16, in a solvent comprising trifluoroethyl trifiuoroacetate. The cloth samples were blotted with paper toweling to remove excess solution and were then dried in anoven at 160 C. for five minutes. The oil repellency, as measured by the 3M Oil Repellency Test, received a rating of 80. The water repellency, as measured by the Spray Test Method, received a rating of 60.

When other homopolymers within the scope of the invention are used to form coatings on porous materials, such as described above, substantially the same results are obtained, i.e., there is imparted to such materials good oil and water repellency properties. Even more significantly, coatings so formed and applied exhibit a high degree of durability and retain their oleophobic and hydrophobic properties even after repeated washings, dry cleaning and long wear. Oil repellency ratings for these materials vary from about 80 up to about with water repellency ratings varying from about 60 to about 70.

The homopolymeric products may also be used to cast elastic, transparent, thermoplastic films by conventional procedures, such as by casting a solution of the polymeric product in a suitable solvent over a smooth surface, evaporating the solvent therefrom, drying the resulting film and stripping the same from the smooth surface. Such films may also be prepared by casting solutions of the corresponding monomers over the smooth surface in a suitable solvent, evaporating the solvent, drying the resulting film and polymerizing in situ by means of heat and small amounts of a conventional initiator. I

The foregoing description is to be taken as illustrative only and the invention is to be limited only by the scope of the appended claims.

We claim: 1. Polyfluoroalkoxy acrylates of the formula:

wherein X is H or CH Y is H or F; Z is H or F; R and R: which may be the same or different, when taken singly, are straight chain perfiuorinated alkyl groups each having from 2 to 11 carbon atoms and, when taken together, form a polyfiuorinated cycloalkyl group possessing 4-6 carbon atoms inclusive; n to or 1; m is 0 or 1; provided that when n is 1, m is 0 and when n is 0, m is 1 and provided that when m is 1, Y and Z are alike; and wherein p is (ll-8.

2. Polyfiuoroalkoxy acrylates according to claim 1 wherein X is H.

3. Polyfluoroalkoxy acrylates according to claim 1 wherein n is 1.

4. Polyfluoroalkoxy acrylates according to claim 1 wherein p is 0-2.

5. Polyfiuoralkoxy acrylates according to claim 1 wherein X is H, n is 1, p is 0-2.

6. Polyfiuoroalkoxy acrylates according to claim 5 wherein the Rf and R groups each have from 6-10 carbon'atoms.

7. 1,3-bis(hexafluoroisopropoxy)isopropyl acrylate.

8. 1,3-bis(heptafluoroisopropoxy)isopropyl acrylate.

9. 1,3-bis(perfluorohexoxy)isopropyl methaerylate.

10. 1,3-bis(perfluorocyclobutoxy)isopropyl acrylate.

11. Polymers comprising recurring polyfiuoroalkoxy aerylate ester units of the formula:

and R f which may be the same or different, when taken singly, are straight chain perfluorinated alkyl groups each having from 2 to 11 carbon atoms and, when taken together, form a polyfluorinated cyeloalkyl group possessing 4-6 carbon atoms inclusive; n is 0 or 1; m is 0 or 1; provided that when n is 1, m is 0 and when n is 0, m is 1 and provided that when m is 1, Y and Z are alike; and wherein p is 0-8.

12. Polymers according to claim 11 wherein X is H.

13. Polymers comprising recurring polyfiuoroisopropoxy acrylate ester units of the formula:

s)zCHOCH2 O LH; CHO( J-( ]X (CFs)2CH0CH2 Li l wherein X is H or CH 14. A polyfluoroalkoxy acrylate homopolymer derived from a monomer having the formula:

wherein X is H or CH 15. 1,3 bis(polyfluoroalkoxy)isopropanols formula:

of the straight chain perfluorinated alkyl groups each having from 2 to 11 carbon atoms and, when taken together,

form a polyfluorinated cycloalky group possessing 4-6 n is O or 1; m is O or 1, provided 0 and when n is 0, m is 1 and 1, Y and Z are alike; and

carbon atoms inclusive; that when n is 1, m is provided that when m is wherein p is 0-8.

16. 1,3-bis(polyfluoroalkoxy)isopropanols according to claim 15 in which n is 1 and p is 0-2.

17. 1,3-bis(hexafluoroisopropoxy)isopropanol.

No references cited.

JOSEPH L. SCHOFER, Primary Examiner. HARRY WONG, 111., Assistant Examiner. 

11. POLYMERS COMPRISING RECURRING POLYFLUOROALKOXY ACRYLATE ESTER UNITS OF THE FORULA: 